Image-receiving element for use in photographic silver halide diffusion transfer process

ABSTRACT

An image-receiving element for use in silver halide diffusion transfer processes, which element comprises a support having coated thereon a diffusion transfer image-receiving layer comprising a colloidal silicon dioxide containing silverprecipitating nuclei dispersed therein, said image receiving layer being overcoated with a layer containing therein polyaddition products derived from a bisacrylamide and a diamine compound, which bisacrylamide is represented by the following general formula

United States Patent [191 Tsuji et al.

[ June 28, 1974 IMAGE-RECEIVING ELEMENT FOR USE IN .PIJQIQQBA HIC SILVEKHALIDE DIFFUSION TRANSFER PROCESS [75] Inventors: Nobuo Tsuji; Takushi Miyazako;

Kinji Ohkubo; Kazunobu Kato, all of Kanagawa, Japan [73] Assignee: Fuji Photo Film Co., Ltd.,

Kanagawa, Japan 22 Filed: Oct. 27, 1971 21 Appl.No.: 193,183

[30] Foreign Application Priority Data 4/1971 Rust ..96/115 F OTHER PUBLICATIONS Polymer, Vol. 11,1970, pp. 88-110.

Primary ExaminerRonald H. Smith Assistant Examiner-John L. Goodrow Attorney, Agent, or Firm-Sugh:rue. Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT An image-receiving element for use in silver halide diffusion transfer processes, which element comprises a support having coated thereon a diffusion transfer image-receiving layer comprising a colloidal silicon dioxide containing silver-precipitating nuclei dispersed therein, said image receiving layer being overcoated with a layer containing therein poly-addition products derived from a bisacrylamide and a diamine compound, which bisacrylamide is represented by the following general formula wherein R is a divalent hydrocarbon group having not more than 10 carbon atoms. The overcoating layer serves as a stripping layer of improved properties.

11 Claims, No Drawings BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to an image-receiving element for use in photographic silver salt diffusion transfer processes.

2. Description of the Prior Art In hitherto known diffusion transfer photographic processes there are used light-sensitive photographic materials comprising a support having coated thereon a dispersion of fine particles .of a light-sensitive silver salt, such as a silver halide in a hydrophilic binder such as gelatin. The light-sensitive layer thereof was exposed to light image-wisely and then contacted with a processing composition containing therein a developing agent to affect development of the exposed layer. At this point, the exposed silver halide in the lightsensitive layer is reduced (developed) to metallic silver.

Concurrently therewith, or subsequently thereto, the light-sensitive element is processed with a silvercomplex forming agent, whereby a water-soluble silver complex is formed by reaction of the unexposed silver halide with the silver-complex forming agent. When, concurrently therewith, an image-receiving element having an image receiving layer containing therein a substance dispersed in a hydrophilic binder, which substance serves as a catalyst for reduction of the abovedescribed water-soluble silver complex (said substance therefore comprising silver-precipitating nuclei or development nuclei), is brought into intimate surface contact with the aforementioned light-sensitive negative layer, the silver complex formed in the lightsensitive layer is, at least in part, transported to the image-receiving layer by diffusion. It is then reduced to silver by the effect of the development nuclei contained therein, thereby forming a positive image having a pattern corresponding to the original.

This process and the materials used therein are disclosed in detail in Chimie et Physique Photographiques" by P. Glaflrides, 3rd Ed., published by Publications Photo-Cinema Paul Montel (1967), pages 469 to 471.

In order to obtain the desired print, the imagereceiving element must be dissociated or stripped from the light-sensitive element. A coating film, usually called a stripping layer, is usually provided on the image-receiving layer to facilitate the dissociation or stripping and to prevent a film of the diffusion transfer processing composition from attaching itself to and remaining on the surface of the processed imagereceiving layer. When the dissociation or stripping is unsatisfactory and/or the processing composition re mains thereon, the image-surface of the imagereceiving element is tainted and the quality of the image is remarkably lowered. Furthermore, in the absence of such a stripping layer on the image-receiving element, the silver images formed on the imagereceiving element frequently undergo deterioration upon storage and/or the highlight areas thereof yellow.

As materials for the aforementioned stripping layer, there have been previously employed, for example,

2 gum arabic, hydroxyethyl cellulose, methyl cellulose, polyvinyl alcohol, polymethacrylate, resins and sodium alginate.

Although the above-mentioned materials are effective to stop processing composition remaining on the surface of the positive print, and to protect the surface of the image-receiving sheet from. being scratched during handling, they often present disadvantages in that the transferred image assumes a metallic luster and/or the maximum density of the positive image is lowered.

SUMMARY OF THE INVENTION CH =CHCONH-R-NHCOCH=CH wherein R is a divalent hydrocarbon group defined hereinafter.

An object of the present invention is to provide the aforementioned image-receiving material which yields a positive print free from deteriorated silver images or yellowed areas even in its highlight areas.

Another object of the present invention is to provide the aforementioned image-receiving material which has a surface protected from being scratched on handling.

DETAILED DESCRIPTION OF THE INVENTION The condensation products which characterize the present invention may be prepared by the poly-addition of bisacrylamide to diamine compound. The representative polycondensation condition is provided in Polymer vo. ll, page 88 (1970).

One of the starting materials, bisacrylamide, may be represented by the following general formula wherein R stands for a divalent hydrocarbon group such as n being a number from 1 to 10,

The other starting material, the diamine compound may be, for example, ethylene diamine, 1,3- propanediamine, hexamethylene diamine, piperadine, xylylene diamine, phenylene diamine. According to our study, the condensation products wherein, above all, ethylene diamine, 1,3-propane diamine or piperidine are used have been found to be most suitable for accomplishing the afore-mentioned objects of the present invention. Furthermore, the lower the number of carbon atoms in the R group in the bisacrylamide, the better the results which are obtained. The intrinsic viscosity [n] of the addition-polymerization products, which reflects the polymerization degree thereof, preferably ranges from 0.005 to 0.5, particularly from 0.01 to 0.1. In this specification, intrinsic viscosity is measured in water at 30 C.

Specific examples of such poly-addition products will be illustrated by the following. (Compound 1) The poly-addition product of methylene bisacrylamide and ethylene diamine having an intrinsic viscosity 11H c Of (Compound 2) The poly-addition product of methylene bisacrvlamide and piperadine having an intrinsic viscosity m c Qf. ,-Q90 (Compound 3) The poly-addition product of ethylene bisacrylan iide and piperidine having an intrinsic viscosity of 0.065.

(Compound 4) The poly-addition products of methylene bisacrylamide and 1,3-propane diamine having an intrinsic viscosity n of 0.070.

These poly-addition products are all soluble in water or alcohols, so that they can be applied, in the form of a solution in water, alcohol or a mixture of water and alcohol, to the surface of an image-receiving element.

The coating weight of the products is in the range of from about 0.1 to about 2.0 g/m preferably from 0.3 to 1.0 g/m 1f the coverage is much less than the recited range, the effect of preventing attachment of the processing composition tends to be lessened while if the coverage exceeds the range, diffusion transfer tends to be inhibited.

As the support for use in the image-receiving element according to the present invention, there may be employed any suitable material used as such supports by the prior art, for exarnple, films or sheets of filmforming resins such as polyethylene terephthalate, cellulose triacetate, polycarbonate, polyvinyl chloride or polyethylene, baryta-coated paper, resin-coated papers, glass plates, metal plates, plates made of earthen ware or like materials.

As silver precipitating nuclei useful in the present invention, there may be preferably employed the normally water-insoluble sulfides, or selenides of Cd, Pt,

Zn, Cu, Co, Ni, Fe, Sn, Au, Ag, etc., or colloidal heavy or noble metal, such as of Au, Ag, Pt, Pd, Hg, etc., having an average size of less than 10 microns, it being desirable that the silver precipitating nuclei in the imagereceiving element be of high activity. In particular, im age-receiving elements utilizing highly active silver precipitating nuclei can be preferentially used as high speed diffusion transfer photographic materials. U.S. Pat. No. 2,698,237 describes a method for preparing such highly active silver precipitating nuclei, wherein a water-soluble metal salt and water-soluble sulfide are admixed in particulate silicon dioxide, thereby forming a precipitate of the resulting water-insoluble metal sulfide. Any other hitherto known techniques for forming such silver precipitating nuceli can be applied to the present invention.

The operable ratio of the silver precipitating nuclei: colloidal silicon dioxide in the layer is within 1:5 to 1:1,000 by weight, preferably 1:50 to 1:200.

The colloidal silicon dioxide which has incorporated therein the silver-precipitating nuclei and also serves as a binder is also known as anhydrous silicic acid, and per se is an acidic substance. When it is dispersed in water, it is in part hydrated to form silicic acid. The pKa and pKa of silicic acid are 9.8 and 12.16 at 30 C, respectively, It is desirable that the silicon dioxide used in the present invention be in the form of particles which are as fine as possible such as less than 1 micron. Examples of silicon dioxides suitable for use in the present invention and commerically available are listed in the follows @1219. In thql s C mn 91 the t b a e show P Maker Trade Name Form pH Monsanto Chemical Co. Santocel 54 4% aqueous dispersion 3.8 do. do. C do. 3.8 do. do. L do. 4.0 do. do. 62 do. 3.8 do. do. FRC do. 3.8 Nippon Aerosil K.K. Aerosil 130 4% aqueous dispersion 3.6-4.3

do. do. 200 do. 3.6 -4.3 do. do. 300 do. 3.6-4.3 do. do. 0 do. 3.64.3 do. do. 380 do. 3.6 4.3 do. do. MOX80 do. 3.6-4.2 do. do. COK84 do. 3.8-4.6 do. do. MOK170 d0. 3.6-4.2 W.R. Grace & Co. Davison Chemical Divisio Syloid 308 5% aqueous dispersion 2.4 do. do. 404 do. 7.0 do. do. AL-l do. 3.8 do. do. do. 3.8 do. do. 978 do. 2.4 do. do. 161 do. 7.0 do. do. 162 do. 7.0 do. do. 244 do. 7.0 do. do. do. 7.0 5.1. du Pont de Nemours Co. Ludox HS-40 40.1% aqueous dispersion 9.6 do. do. HS-30 30.1% do. 9.8 do. do. LS 30.1% do. 8.3 do. do. AS 30.1% do. 9.4 do. do. AM 30% do. 9.] do. do. SM 30% do. 9.9 Nissan chemical Snowtex 20 2()-21% aqueous 9.5- Industries, Ltd. dispersion do. do. 30 30-31% do. 9.5-10.S do. do. 40 40-41% do. 9.5-10.5 do. do. C 20-21% do. 8.5-9.0 do. do. N do. do. 8.0-9.5 do. 0 do. do. 3.0-4.0

ivalues of aqueous dispersions of the respective silicon followed by drying and providing on the resulting layer the stripping layer containing the aforementioned polyaddition products, the effective and preferred combined thickness of their layers being within 0.1 to microns, more preferably 0.5 to 5 microns. To the polyaddition product layer may also be incorporated surface active agents such as saponin, and to silicon dioxide layer may be incorporated such a surface active agent, a toning agent such as triphenyl-S-mercapto tetrazole or benzimidazole, a reducing agent such as phenidone, polyethanolamine, ethanol amine, glycerine, hydroquinone etc.

The thus obtained image-receiving element can accomplish the aforementioned objects and is very useful as a diffusion transfer photographic material.

The present invention will be further explained in detail with particular reference to the following Comparison Examples and Examples.

COMPARISON EXAMPLE 1 An aqueous dispersion of silver-precipitating nuclei was prepared by mixing the following ingredients:

5'7: by weight, aqueous solution ofSantocel 54 (trade name. silicon dioxide manufactured by Monsanto Chemical Co.) 250 cc 2% by weight, aqueous solution of lead acetate (trihydrate) l.5 cc 3% by weight, aqueous solution of cadmium acetate (dihydrate) 2.3 cc 5% by weight, aqueous solution of zinc nitrate (pentahydrate) 5.0 cc 3% by weight, aqueous solution of sodium sulfide (monohydrate) 1.0 cc 6% by weight, aqueous solution of saponin 5.0 cc

Water 1,860 g Sodium salt of carboxymethyl cellulose l 17 g Sodium sulfite (anhydrous) 78 g Sodium hydroxide 74.6 g Sodium thiosulfate (crystalline) 14.5 g Citric acid 38.5 g Hydroquinone 52 g The negative element and the image-receiving element were kept in contact with each other for a period 6 of 15 seconds to effect the diffusion transfer of the images, after which the image-receiving element was stripped off the negative element. The resulting positive print on the image-receiving element was covered with a film of the processing composition and tainted brown.

Comparison Example 2 A solution having the following composition:

Gum arabic (lwaki Seiyaku Co., Ltd.) 2.0 g Distilled water I00 cc 6% aqueous solution of saponin 2.0 cc

was applied onto the coating of the image-receiving element prepared in Comparison Example 1 at a coverage of 20 cc/m, and then dried. The image-receivingelement thus obtained was then processed in the same manner as in Comparison Example 1.

After 15 seconds of processing, the image-receiving element was separated from the negative element and it was found that the processing composition film adhered only to the negative element, but not to the image-receiving element. However, the maximum density of the resulting positive images was 0.80 in terms of reflection density. Furthermore, the transferred images in the areas of high density assumed a metallic luster.

EXAMPLE 1 On top of the coating of the image-receiving element prepared in Comparison Example 1 there was coated an aqueous solution having the following composition:

Poly-addition product of methylene bisacrylamide and ethyler ediamine (intrinsic viscosity n 0.085,

see below with regar to the synthesis thereof) 2.0 g 6% aqueous solution of saponin 1 N aqueous caustic soda solution to adjust the pH to The coverage was 20 cc/m The element was then dried, thereby forming a stripping layer. Synthesis of the above-described poly-addition product lar weight was 350 and the intrinsic viscosity [111 0 The image-receiving element obtained as described above was then diffusion transfer processed in the same manner as Comparison Example 1,. thereby obtaining a positive print without any processing composition remaining thereon.

The maximum density of the transferred positive image was 1.50 in terms of reflection density, and no metallic luster was observed even in the areas of high density.

EXAMPLE 2 On top of the coating of the image-receiving element prepared in Comparison Example 1, there was coated an aqueous solution having the following composition:

Poly-addition product of methylene bisacrylamide and piperazine (intrinsic iscosity n 0.090) 2.5 g l Distilled water I cc O 6% aqueous solution of saponin 2.006

tallic luster was observed even in areas of high density.

EXAMPLE 3 Poly-addition product of methylene bisacrylamide and IJ- r panedIamme (intrinsic viscosity n 0.070) 20 g Distilled water 100 cc 2.0 cc

6% aqueous solution of saponin l N aqueous caustic soda solution to adjust the pH to 7.0 at a coverage of 20 cc/m The element was then 40 dried, thereby forming a stripping layer.

The image-receiving element thus obtained was then diffusion transfer processed in the same manner as Comparison Example 1, thereby obtaining a positive print without any processing composition film remaining thereon.

The maximum density of the transferred positive image was 1.00 in terms of reflection density, and no metallic luster was observed, even in the areas of high density. I

As is evident from the above-described examples, the image-receiving element coated with the compounds of 'the present invention are remarkedly superior to the hitherto known elements coated with other compounds, in that developing composition films are neither attached nor left on the positive element of the invention, and the maximum density of the transferred images is high.

Furthermore, in an image-receiving element having coated thereon the compounds of the invention any scratching during handling is avoided, and no processing composition film remains on the positive surface, so that any deterioration of the resulting silver images or brown-tainting by oxidation products contained in the processing composition will not occur.

Although the invention has been described in considerable detail with reference to certain embodiments thereof, it will be understood that variations and modifications can be effected without departing from the spirit and scope of the invention as described hereinabove and defined in the appended claims.

What we claim is:

1. In an image-receiving element for use in silver halide diffusion transfer photographic processes which comprises a support having coated thereon a diffusion image-receiving layer comprising a colloidal silicon dioxide containing silver-precipitating nuclei dispersed therein, the improvement which comprises said imagereceiving layer being overcoated with a layer containing poly-addition products derived from 21 bisacrylamide represented by the following general formula:

CH ==CHCONH-RNHCOCH=CH and a diamine compound selected from the group consisting of ethylene diamine, 1,3-propane diamine, hexamethylene diamine, piperazine, xylene diamine and phenylene diamine, said silver precipitating nuclei being a member selected from the group consisting of water-insoluble metal sulfides, metal selenides, colloidal heavy metals and colloidal noble metals.

2. The image-receiving element as claimed in claim 1 wherein said bisacrylamide is methylene bisacrylamide and said diamine compound is ethylene diamine.

3. The image-receiving element as claimed in claim 1 wherein said bisacrylamide is methylene bisacrylamide and said diamine compound is piperazine.

4. The image-receiving element as claimed in claim 1 wherein said bisacrylamide is ethylene bisacrylamide and said diamine compound is ethylene diamine.

5. The image-receiving element as claimed in claim 1 wherein said bisacrylamide is methylene bisacrylamide and said diamine compound is l,3-propanediamine.

6. The image-receiving element as claimed in claim 0 1 wherein said poly-addition products have an intrinsic viscosity n C of from 0.005 to 0.5.

7. The image-receiving element as claimed in claim 1 wherein said image-receiving layer is overcoated with a poly-addition products in the form of a solution in a member selected from the group consisting of water, an alcohol or a mixture of water and an alcohol.

8. The image-receiving element as claimed in claim 1, wherein said image-receiving layer is overcoated with the poly-addition products at a coverage of from 0.1 to 2.0 g./m

9. The image-receiving element as claimed in claim 1 wherein the weight ratio of said silver precipitating nuclei: said colloidal silicon dioxide varies from 1:5 to 1:1000.

10. The image-receiving element as claimed in claim 1 wherein said colloidal silicon dioxide has a particle size of less than 1 micron.

heavy and noble metals selected from the group consisting of gold, silver, platinum, palladium and mercury, said silver precipitating nuclei having an average particle size of less than 10 microns.

UNITED STATES ?ATEN'E OFFICE CERTIFICATE OF CORRECTION Patent C Dated June 28 1974 Inventor(s) N0bu0 TSUJI et 8.1

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected'as shown below:

INTI-IE CLAIMS:

Column 8, claim 1, line 25 change the right-hand structural formula to the following:

Signed and sealed this 11th ay Qi' March 1975.

(SEAL) Attest: M T

C. iEAfiLiHALL DAMN BUTTE C Commissioner of Patents Attescing Officer C v and Trademarks 

2. The image-receiving element as claimed in claim 1 wherein said bisacrylamide is methylene bisacrylamide and said diamine compound is ethylene diamine.
 3. The image-receiving element as claimed in claim 1 wherein said bisacrylamide is methylene bisacrylamide and said diamine compound is piperazine.
 4. The image-receiving element as claimed in claim 1 wherein said bisacrylamide is ethylene bisacrylamide and said diamine compound is ethylene diaMine.
 5. The image-receiving element as claimed in claim 1 wherein said bisacrylamide is methylene bisacrylamide and said diamine compound is 1,3-propanediamine.
 6. The image-receiving element as claimed in claim 1 wherein said poly-addition products have an intrinsic viscosity nH O30 C of from 0.005 to 0.5.
 7. The image-receiving element as claimed in claim 1 wherein said image-receiving layer is overcoated with a poly-addition products in the form of a solution in a member selected from the group consisting of water, an alcohol or a mixture of water and an alcohol.
 8. The image-receiving element as claimed in claim 1, wherein said image-receiving layer is overcoated with the poly-addition products at a coverage of from 0.1 to 2.0 g./m2.
 9. The image-receiving element as claimed in claim 1 wherein the weight ratio of said silver precipitating nuclei: said colloidal silicon dioxide varies from 1:5 to 1:1000.
 10. The image-receiving element as claimed in claim 1 wherein said colloidal silicon dioxide has a particle size of less than 1 micron.
 11. The image-receiving element as claimed in claim 1 wherein said silver precipitating nuclei are selected from the group consisting of water insoluble sulfides and selenides of cadminum, platinum, zinc, copper, cobalt, nickel, iron, tin, gold and silver and colloidal heavy and noble metals selected from the group consisting of gold, silver, platinum, palladium and mercury, said silver precipitating nuclei having an average particle size of less than 10 microns. 